Method for printing textiles using a precoat containing {62 -1,4 glucan

ABSTRACT

Pre-treating of textile fabrics with an aqueous dispersion of finely-divided Beta -1,4 glucan particles and a water-soluble binder to provide sharper and deeper colored prints from a printing process which employs a steam treatment.

United States Patent Mizuma et al.

METHOD FOR PRINTING TEXTILES USING A PRECOAT CONTAINING [El-1,4 GLUCAN Inventors: Noriaki Mizuma, Tokyo; Yuzo Yokota, Oi-Machi, both of Japan FMC Corporation, Philadelphia, Pa.

The portion of the term of this patent subsequent to July 25, 1989, has been disclaimed.

Filed: Feb. 7, 1972 Appl. No.: 224,246

Related U.S. Application Data Continuation-impart of Ser. No. 28,144, April 13, 1970, abandoned.

Assignee:

Notice:

U.S. CI 8/62; 8/91 Int. Cl D06]; 1/48 Field of Search 8/91, 62, 167

References Cited UNITED STATES PATENTS 10/1932 Dreyfus 8/167 OTHER PUBLICATIONS Exporte Weissbein. Paper No. 18. in Patent File of Pat. No. 3,679,351, 4 pages with 4 pages attachment listing discontinued dyes.

Primary Examiner- Donald Levy [57} ABSTRACT Pre-treating of textile fabrics with an aqueous dispersion of finelydivided [3-1.4 glucan particles and a water-soluble binder to provide sharper and deeper colored prints from a printing process which employs a steam treatment.

3 Claims, N0 Drawings METHOD FOR PRINTING TEXTILES USING A PRECOAT CONTAINING B-l,4 GLUCAN This application is a continuation-in-part of copending application Ser. No. 28,144, filed Apr. 13, 1970 now abandoned.

This invention relates to a method for the treatment of textile fabrics prior to printing, especially fabrics of hydrophobic fibers, synthetic fibers and fabrics of blends of hydrophobic and hydrophilic fibers, to improve sharpness, uniformity and color yield for dyeing.

In order to keep pace with developments in the synthetic fiber industry and the marked progress of techniques of their fiber blending and weaving, there is an urgent need for improvement in the printing art and studies of all aspects thereofare being made. Nevertheless, under the present state of conditions where there are infinite varieties of print material and the require' ments for printability have become more and more exacting, many unsolved problems remain. It is a known fact that the improvement ofcolor printing characteris tics including sharpness ofbleeding", uneven printing and color yield are urgent problems. It has heretofore been known that, in hydrophobic articles such as in synthetic fibers or their blended or mixed fabrics, lack of affinity between aqueous dye-paste and fabrics for printing produces a serious drawback at the time of printing and especially steaming. Excess water in the dye-paste floats on the surface of the textile fabric, causing a capillary phenomenon, externally moving out of the printed pattern, and thus producing bleeding. Furthermore, such excess of water, upon being subjected to printing pressure from rollers or squeezers, easily reaches to the back of the fabric. And, a result of such osmosis, not only is there uneven dyeing. but also less residual adhesion of dye-paste on the fabric, thus deteriorating color yield.

It has now been discovered that the above printing defects may be substantially overcome and high printability secured with a specific pre-treatment for textile fabric to be printed.

The method of this invention comprises coating a textile fabric with an aqueous dispersion consisting essentially of finely-divided, water-insoluble organic particles at least about 90 percent, preferably 99 percent by weight consisting of B-l,4 glucan and a watersoluble binder, drying said coating, printing a design on said fabric with a colored printing paste, treating the printed textile with direct application of steam, washing the textile to remove said organic particles and drying the textile.

This is an improvement over the disclosure of U.S. Pat. No. 3,259,537 to Orlando A. Battista.

The waterinsoluble, organic material is originally derived from cellulose-containing plant life, in most instances, wood, cotton, and bast or leaf fibers. In general, materials obtained from a hole-cellulose source are most useful, for example. ramie, flax, hemp, cotton, processed cellulose-containing material, for example, cotton linters, purified cotton, wood pulps such as bleached sulfite and sulfate pulps, regenerated forms of cellulose including rayon and cellophane, and the like. If the source material is too low in B-l,4 glucan con tent, it is purified to remove nonessential or undesirable components such as pentosans, galactomannans, glucomannans, and the like, to provide a product containing at least and preferably at least about 99 percent of B-l,4 glucan.

The method of achieving the low particle size is not critical from the standpoint of this invention and will generally include, for example, mechanical disintegration, a combination of chemical degradation and mechanical attrition, chemical treatment only, precipita tion from solution. and chemical regeneration. It is preferred on the basis of practical utility, that a combination of chemical degradation and mechanical attrition be used in forming the specified partical size of the water-insoluble 84,4 glucan-containing material.

Hereinafter, the tern cellulose" will be used to represent ,B- l ,4 glucan-containing materials for ease of explanation and illustration.

Chemical degradation of the cellulose material is brought about in a known manner to facilitate disintegration, for example, the material may be subjected to acid or alkali hydrolysis, or enzymatic treatment. One specific method of obtaining the desired result is reported in U.S. Pat. No. 2,978,446, issued Apr. 4, 1961, to Orlando A. Battista et al, wherein cellulose is subjected to a 2.5 normal aqueous solution ofhydrochloric acid at boiling (about C.) for 15 minutes. This more drastic hydrolysis treatment provides a material which may be readily mechanically attrited in an aqueous medium with a nominal amount of energy. Similar treatments with mineral acids or alkali under more or less drastic conditions will produce attritable degraded cellulose using nominal or increased energy for disintegration of the material to the proper particle size.

The type of starting material prior to chemical degra dation will also determine the amount or input energy for attrition of the cellulose to obtain the desired particle size, For example, dilute hydrochloric acid hydrolysis of regenerated forms of cellulose will produce a material substantially all of which can be attrited to the desired particle size by merely dispersing the same with a conventional electrically driven kitchen beater in an aqueous medium for a few minutes. Other forms of ccllulosc, for example, wood pulp and cotton linters, after a similar hydrolysis treatment must be attrited with the same or more efficient equipment for at least one half hour or more in an aqueous medium to provide a material at least a portion of which is within the desired particle size range. Mechanical attrition may be carried out by known techniques using for example, kitchen mixers. blenders, planetary mixers, ball mills, attrition mills, sonic mixers, high speed shearing devices and the like. In addition, the material may be forced through a multiplicity of fine holes whereby it is subjected to a shearing action first by passage through said holes and thereafter by rubbing together of the various particles under the influence of applied force. The disintegration is preferably carried out in the presence of an aqueous medium to appreciably reduce the energy necessary to produce smaller particle sizes. The attrition should be extended to produce amass hwerein at least 30 percent of the particles are less than 1 micron and preferably over 80 percent of the particles measure no greater than about 0.4 micron. Particles having a size, for example, as small as 0.0l micron are useful for this invention.

As previously stated, regenerated forms of cellulose, for example, regenerated cellulose film, are easily brought to the prescribed particle size after the controlled acid hydrolysis by merely dispersing the wetcake material in water with a mixer. This will produce a stable dispersion wherein the dispersed particles are substantially all less than the prescribed 0.4 micron size. When wood pulp, cotton linters, and similar cellulose materials of greater molecular weight are hydrolyzed under controlled conditions and mechanically attrited in an aqueous medium, many larger particles are present along with the desired small particles. When these cellulosic materials are dried after attrition they are difficult to redisperse in water. It has been found that this type of material may be advantageously combined with a minor proportion of a specific barrier material to provide a readily redispersible mass.

Briefly, the barrier material is a specified sodium salt of carboxymethyl cellulose having a degree of substitution of from about 0.60 to about 0.90, and preferably having a viscosity in centipoises at 25C. in a 2 percent aqueous solution of less than l8 up to about 800. The barrier may be combined with the finely-divided cellulose by drying a suspension of the cellulose particles in the presence of about to percent of the barrier material. The combination of barrier and cellulose particles is effective for the purpose of this invention.

The finely-divided material can be used in its originally dispersed form or it may be dried to a powdery material for example, by air or spray drying techniques and then redispersed.

When the finely-divided cellulose is dried, eg. by spray drying, it tends to agglomerate into larger particle sizes in the range of 50-l00 microns and greater. To redisperse this material in water, if it has not been com bined with CMC as disclosed above, high shear or mixing energy must be used.

An aqueous dispersion of this finely-divided cellulose is coated on textile cloth for printing employing a suitable method such as padding, coating, spraying, etc. in the presence such as water-soluble high polymer, e.g. polyvinyl alcohol, rice starch. wheat starch, natural gums, artificial gums, eg the sodium salt of carboxymethyl cellulose, or mixtures of these in an amount preferably ranging from about 0.5 to about 5 percent based on the weight of the aqueous dispersion. The textile is then dried and put to printing. In this case, the addition of finely-divided cellulose to the textile is in an amount sufficient to improve sharpness of printing thereon after a direct application of steam thereto, preferably from about 1 to about 10 percent based on the weight of the aqueous dispersion. The pre-treated cloth fabric thus obtained has suitable water absorbency and water retention mainly on its surface layer, absorbing any excess of water in the dye-paste and further preventing capillary phenomenon. Consequently, it is possible to develop in an exact manner a clear pattern having excellent sharpness by holding down bleeding, as well as providing uniform printing without uneven dyeing. Furthermore, there is no limitation in the application ofthis printing method to any of the known printing processes such as hand printing. roll printing, screen printing and so forth, which set the printing on the fabric by direct application of steam. e.g. at l00-l50C. for a few minutes up to an hour. Since the coating of finely-divided cellulose comes off cloth surfaces casily by ordinary washing, the practical value is high without causing any trouble in appearance or texture of the textile fabric.

The invention is further illustrated by means of examples as follows:

EXAMPLE I To l00 parts of water were added wheat starch, polyvinyl alcohol and finely-divided cellulose in a ratio indicated in Table l, and the mixture was fully mixed and agitated to give four types of treating solutions. The finely-divided cellulose was prepared by the acid bydrolysis and attrition of wood pulp to obtain a product dispersed in an aqueous medium wherein all of the cellulose particles were less than micron. This dispersion of finely-divided cellulose containing 10 percent of a CMC having a D8. of 0.75 was spray dried to obtain a powdery substance having an average particle size of -90 microns. Polyester textile fabrics were dipped in each solution, pressed between rolls at roll pressure of 2 kg/cm then dried for 2.5 minutes on a pin tenter at l05C. Thus, pretreatment was effected.

Next, using a standard type screen having gauze of mesh, the aforementioned pre-treated fabrics were color printed with a printing paste using a screen pro cess, air-dried, heated by direct application of steam for 20 minutes and, after washing with water, scoured for finishing. For comparisons sake, the same fabric, not having been subjected to the pre-treatment process, was printed and after-treated in an identical manner.

The printing paste used for this screen printing had the following composition:

Dye Color index, Disperse Blue 98 15 grams Thickener Locust bean gum 20 grams Solubilizer Thioethylene glycol 2 grams Water 963 grams TOTAL [000 grams In Table II and the following examples, the sharpness of printing is represented by the height of a blank triangle reproduced by printing using a standard 95 mesh screen, the original triangle pattern having dimension of 0.3 cmv along the base and 10 cm. in height. A greater height of the reproduced triangle indicates better sharpness, the best sharpness being represented by a measurement of 95 mm. for the printed triangle. The dye bleeding after printing and direct steaming is determined by the length of the base of the above-mentioned triangle. Accordingly, a greater length of the base indicates a greater degree of bleeding. The optimum bleeding condition is represented by a measurement of 2.7 mm. for the base of the printed triangle.

Pre-lrcated cloth TABLE ll-Continued Sharpness Bleeding Even dyeing Color (mm) (mm) printability Yield with A solution 81 4.5 poor lightly dyed Pre-treated cloth with B solution 87 3.3 good slightly deep dyed Pre-treated cloth with C solution 89 3.2 good deeply dyed Pre-treated cloth with D solution 89 32 good deeply dyed EXAMPLE ll A solution (treating solution E) consisting of two parts of polyvinyl alcohol added to lOO parts of water and another dispersed solution (treating solution F) consisting of parts of finely-divided cellulose added to treating solution E were prepared.

The finely-divided cellulose was prepared by the acid hydrolysis and attrition of regenerated cellulose waste to obtain a product dispersed in an aqueous medium wherein 66 percent of the cellulose particles were under 0.2 micron and substantially all of the remainder were under I micron. This dispersion was spray dried to provide a powdery substance having an average particle size of 50-75 microns. Using a roll coating machine, nylon fabrics were coated with each solution and dried for 2.5 minutes on a pin tenter, thereafter given to printing in a similar manner as described in Example I except that the printing paste had the following composition.

Dye Color Index, Acid Red 1 l7 [5 grams Thickener Locust bcan gum l5 grams Solubilizer Urea 2 grams Acid generator Ammonium sulfate 5 grams Water 963 grams TOTAL 1000 grams The result is observed with naked eyes, judged, and indicated in Table III. For comparisons sake, printing was made on a cloth not subjected to pre-treatment.

Color yield referred to in the table above means the measurement of transparency determined by first cut ting a given quantity of printed part of each sample, ex tracting with pyridine solution, and measuring the transparency of extract solution with a photoelectric photometer. Thus, greater the value, the lower the color yield. The same applies hereafter.

EXAMPLE Ill Mixed with 100 parts of water were sodium salt of carboxymethyl cellulose (CMC) and cellulose crystallite aggregates in a ratio indicated in Table IV, then agitated to provide a treating solution. Following the pretreatment of nylon fabric with said treating solution similarly as done in Example l, the nylon fabric was printed with a printing paste similar to that of Example ll, using a roll printer, air-dried, heated by direct application of steam, washed and scoured. The results shown in Tables V and VI reveal excellent even printmg.

TABLE IV Treating CMC Cellulose crystalline solution (parts) aggregate (parts) G 2 t) H l 2 l 2 4 .l 2 6 TABLE V Even Sharpprint Color ness Bleeding ability Yield Non-pre-treated cloth poor poor uneven lightly dyed Pre-trcated cloth with Marked hleedlightly treating solution G poor ing in steaming une\ en dyed Pre-treated cloth with slightly deeply treating solution H poor good good dyed Pre-treatcd cloth with ver) deeply treating solution l good good good dyed Pro-treated cloth with deeply treating solution J good good good dyed TABLE VI Color Sharpness Bleeding Yield (mm) (mm) (fi Non-pre-trcated cloth 7) 4.2 48 Pre-treated cloth with treating solution G 78 4.3 52 Pre-treated cloth with treating solution H 3.4 42 Pre-treated cloth with treating solution l 88 3.l 4] Pre-treated cloth with treating solution 1 88 3.2 4l

The above two tables show that the use of a watersoluble polymer alone such as CMC does not improve the print pattern as compared to the non-pre-trcated cloth while the combination of the watensoluble polymer and the finely-divided cellulose give great improvement.

Various changes and modifications may be made practicing this invention without departing from the spirit and scope thereof and therefore the invention is not to be limited except as defined in the appended claims.

We claim:

1. A method of printing textile fabric which comprises coating said textile fabric with an aqueous dispersion consisting essentially of finely-divided, waterinsoluble organic particles at least about 90 percent by weight consisting of B-l.4 glucan and a water-soluble binder, drying said coating, printing a design on said fabric with a colored printing paste, treating the printed textile with the direct application of steam. washing the textile to remove the dried coating and drying the textile.

2. The method of claim 1 wherein the finely-divided to percent based on the weight of the dispersion. organic particles are present in the aqueous dispersion in an amount ranging from about 1 to 10 percent based on the weight of the dispersion and the water-soluble binder is present in an amount ranging from about 0.5 5

3. The process of claim 1 wherein the textile fabric comprises hydrophobic fibers.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 1 3,897,204-

DA I July 29, 1975 INV I Noriaki Mizuma and Yuzo Yokota it is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Col. 1, line 41, "specific" should read specified-. Col. 2, line 13, "tern" should read term;

line 58, "hwerein" should read where1n-.

Signed and Scaled this second Day of Danube-r1975 [SEAL] A nest:

RUTII C. MASON C IAISIIALL BARN Arresting Officer Commissioner afferent: and Tndenurks 

1. A METHOD OF PRINTING TEXTILE FABRIC WHICH COMPRISES COATING SAID TEXTILE FABRIC WITH AN AQUEOUS DISPERSION CONSISTING ESSENTIALLY OF FINELY-DIVIDED, WATER-INSOLUBLE ORGANIC PARTICLES AT LEAST ABOUT 90 PERCENT BY WEIGHT CONSISTING OF B-1, 4 GLUCAN AND A WATER-SOLUBLE BINDER, DRYING SAID COATING, PRINTING A DESIGN ON SAID FABRIC WITH A COLORED PRINTING PASTE, TREATING THE PRINTED TEXTILE WITH THE DIRECT APPLICATION OF STEAM, WASHING THE TEXTILE TO REMOVE THE DRIED CATING AND DRYING THE TEXTILE.
 2. The method of claim 1 wherein the finely-divided organic particles are present in the aqueous dispersion in an amount ranging from about 1 to 10 percent based on the weight of the dispersion and the water-soluble binder is present in an amount ranging from about 0.5 to 5 percent based on the weight of the dispersion.
 3. The process of claim 1 wherein the textile fabric comprises hydrophobic fibers. 